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The photo‐initiated defluorination of iridium hexafluoride (IrF6) was investigated in neon and argon matrices at 6 K, and their photoproducts are characterized by IR and UV‐vis spectroscopies as well as quantum‐chemical calculations. The primary photoproducts obtained after irradiation with λ=365 nm are iridium pentafluoride (IrF5) and iridium trifluoride (IrF3), while longer irradiation of the same...
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